Plant growth regulation



Patented May 5, 1953 PLANT? CmRQW TH REGULATION Nathaniel Tischler, Palmyra, N. 3., assignor to Sharples Chemicals Inc.,, a corporation oft Dela-- ware Nc Drawing, Application November 15,1951, Serial No. 256,599

This invention pertains to new and improved compositions of matter-Which are used for treati'ng growing plants to alter the normal life cycle of said plants with adyantageous results. It is particularly concerned with phytoto'gic' ccmpositions which contain as active ingredient, that is, asplant response agent, one" or more alkyl hydrogen' 316 endoxohexahydrophthalates of exo c'is isomeric configuration and conforming structurally to the formula t i on c-on Cnq pn O H'zC cn.

in which R represents a primary or secondary allcyl radical having, from! 1 to; 8. carbon 3113011183 as Wellas with compositions. whichwhen the presencetot water. yield anionsof' such acidse. gr, salts. or said acids.

The invention is concerned more particularly with. the. eXo-cis isomeric form of theabavecompounds. as. active ingredients.v

For convenience. and to avoid. repetition; all references made herein. to; active ingredients. of the. invention are tobe construed as meaning, the exo-cis form.

Examples of the radical R, in the foregoing formula are methyl, ethyl, n-propyl, n-butyl, n-amyl, n-hexyl, n-heptyl, n-cctyl, isobutyl, isoamyl, isohexyl, isopropyl, se.c.-buty1, l-methylhutyl, 1 ,3 dimethylbutyl', diisopropylmethyl, l methylheptyl, and similar primary and. secondary alkyl radicals.

It is pointed out that the mono-alkyl esters of the invention are also; monoca'rboxylic' acids, and that such acids. undergo reactions Which-are characteristic of monocarhoxylic acids generally, including neutralization with organic or'inorganic bases to" form salts;

Phytotoxic' compositions containing at least one of the aforesaid acids, per'se or in chemically equivalent form, are highly eiiective for'the. purpose, and it is a. feature of. this invention to providecompositinns containing the above active ingredients. in admixture with simple, readily available materials which enhance, or. intensify the plant response activity 01. the-abcve active iiigredients. These and other features will become apparentto' personsskilled in theart as the specifi'cation proceeds; I V

CIT-pending application Serial. N 0.. 81,026, filed lil'azrch 11;, 19429, by Nathaniel Tischler and lilrn'e's'tv P; Bell, and issued as U". S. Patent No. 2,576,080 on Ndv'ezrrlcer 20, 1951?, teaches the efiicacy' ofthe 3,G-endoxohydrhphthalic acids and their derivatives in bringing about useful plant response effects such as leaf abscission (partial or complete), blossom thinning; vine-kill, total 2 destruction or the plant. or adventitious root formation, the particular plant: response manitested depending? to a. large extent uponthe applied concentration of. the response agent; technique" of application, and the: species and degree of maturity of the plant undergoing treatment.

Theu's'e of thealkyl hydrogen 3tb' endhxchexahydrophthalates represented by'theabove formulai, pers'e or eq-uiva1entform, forplant response purposes: is: particularly described and claimed in the (sic-pending a plicaticn: of Nathaniel 'I-i'schler and Ernest PL Bell, Serial Ne. 256,598 filed of even date herewith. application is a continua t'i'onein parfi of sai first mentioned application.

The aboveementiohed compounds as applied to plants may be" in the form: of the acids per se or in chemically'equival'ent:ibrm; such as water--s cluh'le salts oi the) acids: Any suchacid: and: its chemically equivalent forms have the common property" of yielding the same species of anions in the presence of water: and hence. are considered to' be equivalent; for plant response purposes.

Thus the acids are the active materialsand this is" so whether they are used: as such' orin chemicallp' equivalent; forms such. as water-soluble salts. 'llheseichan'gcs at the carbonyl groups are mere changes in. form rather than changes in s'u'hstance.

Among. thezwater sclublesalts ofparticular interestrtheresmapbeimentipnedzsodiumpctassium, ealciin-m,. strontium; magnesium; aluminum, iron, cobalt, nickel; zinc, cadmium. mercury, copper, and ammoniurmsalts; mon'o1-, di-,..and trialkylammenium salts; monodi:=,. and: trialkancl'amm'oniumi salts. and: mixed alkylalkanolammonium salts which. are: Nf-swbstituted in. the" ammonium radical from. 2111c: 3i radicals of the type indicatedi;

Burning new to'z the present invention', in: which alkyl' hydrcgem 3,6. endoxohexahydrophthalates (-per se' on im equivalent. formy of the kind described above. are. the active plant response ingredients: of my new" compnsiti'ons, it is pointed out: that. said acids are appreciably soluble in water; Ill-1e other forms are. alsowater-soluble. Shine on them; are: highly soluble, while others have a-lesser-degree of: solubility. However, it is preferred to employ compounds having a solubility int Water to the extent ofi'at" least 011% by weight, and still more particularly ofat least 1% hy'weieht'.

Water solubility is desirable so that anions are formed when theacids, per se or chemically equivalent mm, are" dissolved in water. The desir'abilit'yof such anions will presently become apparent.

Thus" the" foregoing active ingredients may be defined as cnmpoundswhich when in" the presence of water yield anions of exo-cis configuration and conforming to the structure in which the meaning of R, is the same as in the above formula which represents the acids.

Although the present applicant does not wish to be bound by any particular theory as to the mechanism whereby useful plant response effects are produced, a considerable amount of experimentation strongly indicates that said effects are brought about by the existence in aqueous media of anions of the type illustrated above. A salient feature of this theory is that any acid of the invention, when applied per se, or in other form, to a living plant, makes the desired anions available to the plant.

The desired anions are made available by virtue of the fact that the acids per se, and their other forms, are water-soluble and ionizable. Therefore, when such a compound is absorbed into the vascular system of a plant, it dissolves in the aqueous plant juices and provides the functioning anions. The resulting physiological activity is believed to be ascribable to the presence of such anions. The acids per se and their equivalent forms may thus be regarded as very convenient media for furnishing the desired anions to susceptible portions of the plant.

It follows, therefore, that the acids per se and their other forms are equally usable, the foregoing compounds being highly effective for the intended purpose.

I have discovered that the amount of the respective compounds used to produce a given plant response effect may be markedly reduced, or the plant response effect obtained with a given amount of active ingredient markedly increased, by admixing with any said compound or compounds, one or more of the group consisting of ammonium and substituted ammonium salts of the strong mineral acids, e. g. of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, e. g. orthophosphoric acid; said salts being either in neutral or acid form. Particular substituted ammonium salts are the alkylammonium salts, alkanolammonium salts, and mixed alkylalkanolammonium salts.

Examples of such salts are ammonium sulfate, chloride, nitrate and phosphate; ammonium acid sulfate; ammonium dihydrogen phosphate and ammonium monohydrogen phosphate; mono-, di-, and trialkylammonium sulfates, chlorides, nitrates and phosphates, having from 1 to 4 carbon atoms in each alkyl radical; mono-, di-, and trialkylammonium acid sulfates and phosphates having from 1 to 4 carbon atoms in each alkyl radical; mono-, di-, and trialkanolammcnium sulfates, chlorides, nitrates and phosphates, having from 2 to 3 carbon atoms in each alkanol radical; mono-, di-, and trialkanolammonium acid sulfates and phosphates, having from 2 to 3 carbon atoms in each alkanol radical; mixed alkylalkanolammonium sulfates, chlorides, nitrates and phosphates, which are N -substituted by from 2 to 3 radicals of the type and carbon content indicated; and mixed alkylalkanolammonium acid sulfates and phosphates which are N-substituted by from 2 to 3 radicals of the type and carbon content indicated.

As pointed out above, the sulfates and phosphates contemplated include both the acid sulfates and phosphates and the neutral sulfates and phosphates, and mixed neutral sulfates and phosphates, that is sulfates and phosphates in which the cations are different.

The preparation of the sulfates, chlorides, nitrates and phosphates may be accomplished by any means known to the art, and suitable methods will be found in the literature.

Examples of acids of the invention are methyl hydrogen 3,6-endoxohexahydrophthalate, ethyl hydrogen 3,6 endoxohexahydrophthalate, npropyl hydrogen 3,6-endoxohexahydrophthalate, butyl hydrogen 3,6 endoxohexahydrophthalate, n-amyl hydrogen, 3,6 endoxohexahydrophthalate, n-hexyl hydrogen 3,6 endoxohexahydrophthalate, n-heptyl hydrogen 3,6-endoxohexahydrophthalate, n-octyl hydrogen 3,6 endoxohexahydrophthalate, isobutyl hydrogen 3,6 endoxohexahydrophthalate, isoamyl hydrogen 3,6- endoxohexahydrophthalate, isohexyl hydrogen 3,6 endoxohexahydrophthalate, isopropyl hydrogen 3,6 endoxohexahydrophthalate, sec.- butyl hydrogen 3,6 endoxohexahydrophthalate, 1 methylbutyl hydrogen 3,6 endoxohexahydrophthalate, 1,3 dimethylbutyl hydrogen 3,6- endoxohexahydrcphthalate, diisopropylmethyl hydrogen 3,6-endoxohexahydrophthalate, and 1 methylheptyl hydrogen 3,6 endoxohexahydrophthalate.

The preparation of the acids per se and their equivalents may be accomplished by any means known to the art, and suitable methods will suggest themselves to persons skilled in chemical synthesis.

For example, the acids may be prepared by reacting equimolar quantities of exo-cis-3,6- endoxohexahydrophthalic anhydride and a primary or secondary saturated, monohydric, aliphatic alcohol, reaction proceeding in accordance with the equation:

wherein R represents a primary or secondary alkyl radical having from 1 to 8 carbon atoms.

In some instances it may be preferred to bring the reactants together in stoichiometric amounts as shown in the foregoing equation, in the presence or absence of inert reaction media, such as hexane, benzene, toluene, etc. In other instances, it may be preferred to employ the alcohol in considerably more than stoichiometric amount, the excess alcohol serving as a reaction medium. However, in order to facilitate recovery of the desired product after the reaction has been completed, gross excesses of alcohol should not be employed.

Reaction sometimes occurs at ordinary temperature, although it is usually helpful to employ somewhat elevated temperatures, such as up to say 0., in order to speed the reaction. Temperatures appreciably greater than 125 C. may be somewhat conducive to side reaction, such as di-esterification, and hence are less preferred.

In some instances (such as when methanol is a reactant) the use of a catalyst is unnecessary acumen and may even be undesirable, while in other instances a small amount of catalyst (e. :g. hydroohlo'ric acid) may be added to themiirture in or- (let to speed the reaction.

It is pointed out that when a substantial excess of the alcohol is present in the reaction mixture, a possible side reaction is ester-ification of the desired alky-l hydrogen 3,6=endoxohexahydrophthalate, i. e., formation of the undesired dialkyl ester (neutral ester) of 3.,6-endoxoheXahydrophthalic acid. In such instances it is advisable to observe the following precautions, in order to avoid the formation of any substantial amount of neutral ester: (-1) the reaction temperature should be maintained as low as is consistent with causing the desired reaction to proceed at a reasonable speed: (2) the reaction time should be as short as is consistent with causing the desired reaction 'to-go to completion; and (-3) no part of the reaction mixture should be r moved during the reaction period.

The amount of additive or intensifier to be admixed "with the "active ingredient ma vary over a very wide range. A small amount will produce a useful intensifying effect, and since some of the 'intensifie'r's employed in this invention are also .good fertilizers, especially in the case of ammonium sulfate, ammonium nitrate,

"and dlainm'onium hydrogen phosphate, I contemplate the use of proportions of intensifier .=1

far in excess of those proportions producing optimum intensifying action.

For practicable purposes, pr'oportions of intensifier to active ingredient of from 1:10 to 20:1, and particularly from 1:2 to 521 are very proportion of intensifier to active ingredient may run quite high, such as up to 100:1, or even "more.

The intensifier and the active ingredient may be admixed in any desired manner such "as by mere mechanical mixing in solid form, or while P in solution in a common solvent such as water. In the latter case the solution may be marketed as such. or if desired, may be dried at temperatures sunlciently low to prevent decomposition of the active ingredient, such as up to say 125 C. In any case, it is preferred to have a solid admixture in finely divided form and su'fiiciently dry to be free flowing.

The admixtures are applied to the crop or plants in any desired manner, such as in the form of a solid, for example, by dusting, or in the form of a liquid, for example, by spraying.

Compositions may be formulated by mixing the admixture containing the intensifier and active ingredient with any desired liquid or solid carriers, such as any of the finely divided solid carriers known in the dusting art, which are preferably of large surface area, such clay, for exam'me, iuilers earth, 'pyrcphyllite, talc, bentonite. hie'seleuhr, diatornaceoue earth, etc. Any of the commercial clays available on the market in finely divided form may be used, and particularly those which are normally -ern aloyed "as insecticide carriers. Commercial clays, I it will be understood, are generall identified by trade names (reflecting the source and mode of processing), of which Homer clay, ileli'te, and Tripoli may be mentioned as typical.

Non-clay carriers which may "be fermented with my admixture include, for example,

5 volcanic ash, calcium carbonate, lime, by-prodnot lienin, lignocel lulose, flour, such as wood, vialnut shell, wheat, soybean, potato, cottonseed, e 'c.

Any desired mixture may be prepared by any suitable method. Thus, if a solid, the active ingre'cli'e'nt may be ground to a fine powder and tumbled together with the intensifier, or the intensiner and the active ingredient may be ground together; alternatively, the active ingredient in liquid form, inclmling solutions, dispersions, emulsions, and suspensions thereof, may bead mixed with the intensifier in finely divided form in amounts small enough to preserve the freefloyti'n'g property of the final dust compositions. or excess liquid may be removed, such as by vaporization, for example, under reduced pressure. The same applies to mixtures of the active ingredient, the intensifier, and any finely divided solid carrier and/or other material.

When solid compositions are employed, in order to obtain a high degree of plant coverage with minimum ooundage per acre, it is desirable that the composition be in finely divided form. Preferably, the dust containing the active ingredient should be sufficiently fine that substantially "all will pass through a 50 mesh sieve, and more particularly through a 200 mesh sieve. Excellent results are obtainable in which the dust composition is comprised predominantly of partieles in the range from '15 to 45 morons. Finer dusts, such as those consisting largely of particles in the range of '5 microns and below have excellent covering ce oacity but are somewhat more subject to drift and are more expensure to prepare.

For spray application the admixture may be dissolved or dispersed a liquid carrier such as water or other suitable liquid.

Aqueous solutions ordisoersions are economical and desirable. in general, the choice of the par ticular liquid carrier employed will be guided somewhat by prevailing circumstances, such "as its availability, its solubility or dispersion -chara'cteristics toward the particular admixture employed, and/or its toxicit toward the plants undergoing treatment. In eneral, water is an excellent liquid carrier.

Thus, spray formulations compr sing the active ingredient in the form of a solution, suspension, dispersion, or emulsion, in aqueous or non aoue- "ous media may be employed.

Emulsions or dispersions of the admixture in the liquid carrier may be prep" red by agitation of the admixture with the carrier. This is com- 'monly done at the time of spraying. Preferably, however, the agitation should take place in the presence of an emulsifying or dispersing agent (surface-active agent), in order to facilita'te thepreparation of said emulsion brdi'sp'ersi'on. Ern'ulsi'iying and dispersing agents are wellknoivu in the art, and include, for example, fatty alcohol sulfates, such as sodium laul'yl sulfate, aliphatic or aromatic sul'fonates, suoh as so! fonated Castor oil or the various alkai'yl sulfonate's (such as the sodium salt of moms ionated no'nyl na hthalene or tertiary *dod cy-l benzene) and. non-ionic ty es or emulsifying" and dispersing oi-gents such as the high rnoiec-uiar weight "allr'yl polygl'ycolet'hers or analogousthioothers such the decyl, dodeoyl tetr'aueoyl poly lycolethers and thioethers containing from 25 to '75 carbon'a'toms.

The use, if desired, of adj'uvants, such aswettine agents and/or humectants, also contemagents more particularly referred to above.

plated in connection with solutions of the admixture, such as water solutions. Any suitable ,wetting agent and/or humectant may be employed for this purpose, such as the wetting Examples of humectants are glycerine, diethylene glycol, ethylene glycol, polyethylene glycols generally, and water-soluble sugars and sugar-containing mixtures, such as glucose, fructose, galactose, mannose, arabinose, xylose, sucrose, maltose, lactose, rafiinose, trehalose, dextrins such as white dextrin, canary dextrin, British gum, etc., honey, molasses, maple syrup, maple sugar, and starch syrups such as corn syrup, etc.

For adjuvant purposes, any desired quantity of wetting agent may be employed, such as up to 250% or more based on active ingredient. For wetting purposes, the amount of adjuvant used may be considered to be that required to impart the desired wetting qualities to the spray solution as formulated, such as approximately 0.05% by weight of the spray solution. The use of considerably larger amounts is not based upon wetting properties, although present, but is a function of the physiological behavior of the Wetting agent after spraying upon the plant.

It should be considered that once the solution has been sprayed upon the plant, the concentration of wetting agent existing upon the plant is in no sense a function of the concentration existing the original spray solution. Thus, evaporation might concentrate the wetting agent considerably, or the presence of dew on the plant surfaces, or of plant juices on the plant surfaces might considerably dilute this agent.

It will, of course, be understood that wetting agents, particularly when in solid form, may be compounded with the admixture when in solid form.

Although the admixture of active ingredient and intensifier may be applied to the growing plant in concentrated form, it is usually desirable to employ liquid or solid formulations, for example, as discussed above, in which the active ingredient constitutes less than 30% by weight of the total, such as less than and even as low as 0.1%. When it is intended that the intensifier shall also have a substantial effect as a fertilizer, it may, of course, be present in very substantial quantity with or without the presence of a solid or liquid carrier.

Other substances than the carrier and/or surface active agent may be included in solid or liquid formulations if desired. Thus, active ingredients other than those disclosed herein and compatible with the admixture may be added if desired for any particular purpose. Also substances may be added to bring about various physical improvements such as the prevention of lumping during storage. or improvement with respect to coverage, moisture adsorption, adherence, etc. Such other active ingredients may be included in said formulations to accomplish various physiological effects. For example, it may at times be expedient to include singly or in combination, substances such as fungicides, insecticides, bactericides, or types of plant response agents other than those agents discussed herein.

In practice of the process as applied to defoliation, the rate of application (i. e. the amount of admixture per crop unit) for best results will depend among other factors upon the species of plants being treated and upon their maturity. In any event, the amount of active ingredient employed for the same plant response effect Will be substantially lower than when th intensifier is not present.

As a rule the more mature the plant at the time of application, the less active material is required. In practice the crop is normally treated for defoliation purposes, 1 or 2 weeks prior to harvesting. In some instances, more than one application may be desirable, especially if heavy rains or winds should occur soon after the application, or to obtain an accumulative effect. Then too, in order to avoid possible injury to any particular crop, it may be desirable for an inexperienced operator to apply the defoliant initially at a relatively low rate, and to follow with a second application if necessary after observation of the first effects, to obtain the degree of defoliation desired.

Use of dosages greatly in excess of the minimum required for good defoliation may result in shock to the plant with attendant injury to the remainder of the plant.

In fact, the plant response agents of the present invention are effective herbicides when used in amounts substantially greater than those required for defoliation, and they may be used advantageously for the killing of plants or vines (as in the case of potatoes) when desired, such as, for the killing of undesired plants, for example, weeds 0r grasses, or for the killing of crops, irrespective of whether such undesired plants or crops are of species which lend themselves to defoliation.

Thus when defoliation is the objective the quantity applied should be sufiicient to cause at least the major portion of the leaves to dry up and/or to drop from the living plant, but insufficient to cause substantial herbicidal action on the plant. On the other hand, when plant killing is the objective, any amount sufiicient for this purpose may be applied. In the latter connection, since different species of plants vary markedly in their relative resistance to herbicidal action, selective killing of plant species may be practiced. Such selectivity may be varied by compounding, such as with adjuvants, for example, wetting agents, in addition to the use of an intensifier.

I am aware of U. S. Patent 2,471,790, wherein certain esters having some similarity to the compounds of the present invention are suggested as active ingredients of insect-affecting compositions. However, in accordance with the teachings of this patent, these prior art esters could not be plant response agents, for as is clearly brought out therein, they may be compounded for application to plants for the destruction of ants, flies, chewing insects, aphids, and other insects. It is stated in the above-mentioned patent that the esters may be used in combination with certain solid fertilizers, but there is no evidence that the insect-affecting properties of the esters are thereby intensified.

I am also aware of the fact that it has been proposed to use certain ammonium salts,- such as ammonium sulfate, in combination with phenolic substances, such as dinitroalkylphenols and pentachlorophenol, for plant response purposes. The purpose of such use of ammonium salts as explained by Crafts and Reiber, Hilgardia, volume 16, pages 487-499, and by Crafts, Science, volume 108, pages -86, is to make available the free phenol at the plant surface from an aqueous solution of a water-soluble salt of said phenol. The phenol in such cases is the active plant response substance and is continuously regenerated at the plant surface from its, water-soluble salt. by virtue of the presence of the ammonium salt. As the. free, phenol is absorbed by the plant, surface, further free phenol is, generated under equilibrium conditions. The plant response eifiect. of" the free phenol is not enhanced or intensified. by such procedure, or in other words, is substan.- tially the same as that obtained by the applica: tion directly to, the plant of a similar quantity of freephenol. In view of the insolubi'lity or the. phenol in; water, this: procedure is, adopted. in. order to make available the use..- f Wateras. a ehi lofor applying the plant. responseaaen he. herbicide, to the plant surfaces,

In the case or my invention, an the. other hand. the plant response effectvv obtainedfrom a given qu nt f active ngre ient is. grea er t an that obtained by the application of the same quantity of the particular active ingredient. to the plant th a s of. my tens fi r. n. act. the. plant; response effect, obtained with the sameq ty' of a e. re e may be incre sed. m y times by the ad ti n Qii ar er 1 12 as of my intensifier. The intensification beg ns to. manifest itself by the addition of a small. pror portion of my intensifier and increasesto apQint f p m m. i t nsificati y t e. addition. o in: creasin p p s of tensii i Fo optimum p n-t response effects, he pro ortion of. intensifier to active ingredient may vary somewhat between specific active ingredients and; between spec fic varie ies of plants und o g treatment... so that the exact proportion for optimum eiiect under all conditions, cannot be given, However, the intensific n. f h plan r sp nse enact. p e ent w a m ll quant y of intensifier is added, and the addition of intensifier beyond the. point at which no further marked increase in intensification is obtained does no harm. and may have a, very useful purpose, such, as whfinthen intensifier is. also a fertilizer.

10 The capital letters are. used to des nate. these p u ds. inTabls. be ow.

A series 1 aqueous. solutions having they followng; respect ve. concentrations. of these respecti e. active. in rcd ntswas. pr pared: 1.962%... 9.125%, and. 0.25

Another series. oi aqueous. solutions... wa Ric- Haired h ng the same. concentrations of: the same. active. n redients as, ind ca ed the. p eseding. paragraph; in addition. each solution of. the. lat er s r es, contained. ammonium sulia a. as. an in ensifier. he Weig t.- ra u 0f inten fier to ac e ing edien being 5:1...

The above iesnentille, solutions were spray: misted. by means. of. a smal DeVilbiss atomizer on... individu l roups. of ixte n potted Dwarf; Horticultural. an plants. at. a sta e of growth at which the first trifoliateleaf was still turled.

Each group oi p ants. was. arran ed uni orm y a 2. foot y 3: foo and 3 m Qf. est-$ 1 kio was spray her on as d cr bed bove: his. ra of. app cat on. co res onds. to a p mat y 6 al ons. per acr tne amou o activ ingred nt. per cre was 0.5, 1.0. and 2.9; ounces. respectively; the amount. of ammonium. sulfate was five times as much as that of the. active ingredient, in each instance.

Isable 1 summarizes observations made five days; after treatment. In the table, the symbols. have following meanings:

. bn=burned adh=adhering PL=primary leaves as, for example; means each of four plants had a single primary leaf abscised; 5B, for example means each of five plants had both primary leaves abscised.

QQlllDQUQ et ycngredisntper-aer 41. .0. 1. .1. 4S; adli BLFIL ;.B. 53; d]; l?L,.,.-lt 1213, 4s; m p1 b1 bu. mod b n,

Awith (NHQgSOi 5B,. 8% adh .1313. 3S; adh- PL- 1513-, 1S; adh PL mo inc od D EXAMPLE. 1.

The following compounds. were employed in this:

test:

A. Methyl sodium 3,6 endoxohexahydrophthalate.

B. Methyl d iso ropy ammouium 3.6.-end i 9 s ahydrophthalate.

A group. of plants was not treated and was kept as. a control, the untreated group being similar to the treated groups. All plants, both treated and untreated, were at the same age and had been grown at the same time and under the same conditions. treated plants and untreated control were again kept under the same conditions and therefore were subjected to com-parable growing conditions. The untreated control plants grew normally.

CQntrol tests using the intensifier in the ab,- sence of active ingredient were conducted. Groups, oi plants. wholly analogous to the above roups were treated with ammonium sulfate solutions; of various. concentrations, using the abovedescribed method; of application. Even at a nsane 9f 5 pounds. or ammonium sulfatepe acre. th plants w re not: attested.

When the active ingredients are used in the After the test was commenced, the

aeevgevn formofthe acids per se, aqueous-solutions con-.

alkanolammonium preferably have from 2 to 3' carbon atoms in each .alkanol radical. The mixed, alkylalkanolammonium salts such as monoalkyl monoalkanolammonium, dialkyl monoalkanolammonium, or monoalkyl dialkanolammonium preferably have from 1 to 4 carbon atoms in each alkyl radical and from 2 to 3 carbon atoms in each alkanol radical.

The alkylammonium salts (neutral salts, and also acid salts in cases where such exist) of the strong mineral acids mentioned herein, such as monoamylammonium, dialkylammonium, or trialkylammonium salts, preferably have from 1 to 4 carbon atoms in each alkyl radical. The alkanolammonium salts such as monoalkanolammonium, dialkanolammonium, or trialkanolammonium preferably have from 2 to 3 carbon atoms ineach alkanol radical. The mixed alkylalkanolammonium salts such as monoalkyl monoalkanolammonium, dialkyl monoalkanolammonium, or monoalkyl dialkanolammonium preferably have from 1 to 4 carbon atoms in each alkyl radical and from 2 to 3 carbon atoms in each alkanol radical.

The following examples apply to both the active ingredient and the intensifier.

Examples of monoalkylammonium salts are the monomethylammonium, monoethylammonium, monopropylammonium, monobutylammonium, monoamylammonium, monohexylammonium, monoheptylammonium, monooctylammonium, monononylammonium, monodecylammonium, monoundecylammonium, monododecylammonium and similar monoalkylammonium salts of such acids.

Examples of dialkylammonium salts are the dimethylammonium, diethylammonium; 'dipropylammonium, dibutylammonium, dia'mylammonium, 'dihexylammonium, methylethylammonium, ethylpropylammonium, propylbutylammonium, butylamylammonium, amylhexylammonium, methylundecylammonium, and similar dialkylammonium salts of such acids.

Examples of trialkylammonium salts are the trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, methyldiethylammonium, ethyldipropylammonium, propyldibutylammonium, methyldiamylammonium, ethyldiamylammonium, methylethylpropylammonium, ethylpropylbutylammonium, and similar salts of such acids.

Examples of monoalkanolammonium salts are the monoethanolammonium, monopropanolammonium, and similar salts of such acids.

Examples of dialkanolammonium salts are the diethanolammonium, dipropanolammonium, ethanolpropanolammonium and similar salts of such acids.

Examples of trialkanolammonium salts are the triethanolammonium, tripropanolammonium, ethanoldipropanolammonium, propanoldieth'anolammonium and similar salts of such acids.

Examples of monoalkyl monoalkanolammonium salts are the methylethanolammonium,

ethylethanolammonium, propylethano1ammoni-.-

um,Ibutylethanolammonium, methylpropanolammonium, ethylpropanolammonium, propylpropanolammonium, butylpropanolammonium and similar salts of such acids.

Examples of dialkyl monoalkanolammonium salts are the dimethylethanolammonium, diethylethanolammonium, dipropylethanolammonium, dibutylethanolammonium, dimethylpropanolammonium, diethylpropanolammonium, dipropylpropanolammonium, dibutylpropanolammonium,

methylethylethanolammonium, methylethylpropanolammoniuxn, ethylpropylethanolammonium, ethylpropylpropanolammonium, propylbutyleth anolammonium, propylbutylpropanolammonium, and similar salts of such acids.

Examples of monoalkyl dialkanolammonium salts are the methyldiethanolammonium, ethyldiethanolammonium, propyldiethanolammonium, butyldiethanolammonium, methyldipropanolam- -monium, ethyldipropanolammonium, propyldisimilar salts of such acids.

As pointed out above the intensifiers contem plated include both the acids salts and the neutral salts, and mixed neutral salts, that is salts in which the cations are different.

The term plant as used herein is understood to I include all portions of the plant, such as the roots, stems, leaves, blossoms, seeds, and fruits.

Among the plants which defoliate naturally and which may be defoliated by the use of this invention, are for example, cotton, potatoes, tomatoes, and beans such as soybeans and lima beans.

Among the noxious weeds against which my compositions may be used as herbicides are the following: bindweed, chickweed, cocklebur, mares tail, shepherds-purse, broad-leaved plantain, wild lettuce, ragweed, spurge, dock, and wild carrot.

As pointed out above, certain of the intensifiers referred to herein are Well-known soil fertilizers, such as ammonium sulfate, ammonium nitrate, and diammonium hydrogen phosphate. It follows that the active ingredients in amounts sufli- "cient to cause the desired plant response action may be compounded with such fertilizer and applied simultaneously therewith. This is particularly applicable to pre-emergence or pre-planting practices for the control of weeds, to postemergen'ce treatment for fertilizing purposes and control of weeds as to such useful crops to which the active ingredients evidence only slight or no herbicidal action, such for example as onions, sugar beets, flax, carrots, and cole crops, and otherwise following agricultural practices. The proportion of intensifier to active ingredient in such cases may be as desired, dependent largely upon the amount of fertilizer to be applied per acre, so as to obtain the desired coverage of active ingredient in admixture with the fertilizer. For example, the proportion of intensifier to active ingredient may range from 10001 or 500:1 to :1 or 200:1.

From the foregoing it can be seen that the endoxo compounds used in the practice of this invention, whether used as the acids or in some other form, are highly effective in regulating the growth characteristics of viable or living plants, and particularly of plants having vascular systems, when used in admixture with my intensifier.

For example, the admixture may be employed to hasten defoliation of plants which defoliate naturally, or may be employed to terminate the life cycle of plants, or may be employed to retard the growing of seeds, or may be employed to selectively stunt or terminate the growth of certain unwanted plants to facilitate and favor the growth of wanted plants, or may be employed to terminate the growth of vines in favor of, or to facilitate harvesting of, the fruits of such vines, etc. Other applications of the invention in the regulation of the growth characteristics of plants will occur to persons skilled in the art upon becoming familiar herewith.

Accordingly, it is to be understood that the particular description is by way of illustration and that the patent is intended to cover by suitable expression in the claims Whatever features of novelty reside in the invention.

This application is a continuationin-part of my copending application Serial No. 161,255, filed May 10, 1950, and issued as U. S. Patent No. 2,576,083 on November 20, 1951.

I claim:

1. A plant response composition comprising a salt of a strong mineral acid with at least one of the group consisting of ammonia, alkyl amines, alkanol amines, and mixed alkyl-alkanol amines, and at least one water-soluble compound the anion portion of which is of exo-cis configuration and conforms to the structure in which R represents an alkyl radical selected from the group consisting of primary and secondary alkyl radicals having from 1 to 8 carbon atoms.

2. The composition of claim 1 in which said salt is an ammonium sulfate.

3. The composition of claim 2 in which said salt is ammonium sulfate.

4. The composition of claim 3 containing a wetting agent.

5. A plant response and soil treating composition comprising a major proportion of a soil fertilizing ammonium salt of a strong mineral acid, and a minor but suiiicient proportion for plant response effect of at least one water-soluble salt the anion portion of which is of exo-cis configuration and conforms to the structure in which R represents an alkyl radical selected from the group consisting of primary and secondary alkyl radicals having from 1 to 8 carbon atoms.

6. A plant response composition comprising a salt of a strong mineral acid with at least one of the group consisting of ammonia, alkyl amines, alkanol amines and mixed alkylalkanol amines, and at least one compound which when in the presence of water yields anions of exo-cis configuration and conforming to the structure in which R represents an alkyl radical selected from the group consisting of primary and secondary alkyl radicals having from 1 to 8 carbon atoms.

'7. A plant response and soil treating composition comprising a major proportion of a soil fertilizing ammonium salt of a strong mineral acid, and a minor but sufficient proportion for plant response effect of at least one compound which when in the presence of water yields anions of eXo-cis configuration and conforming to the structure in which R represents an alkyl radical selected from the group consisting of primary and secondary alkyl radicals having from 1 to 8 carbon atoms.

8. A method for inducing plant response in a living plant, comprising applying to said plant a composition comprising a salt of a strong mineral acid withv at least one of the group consisting of ammonia, alkyl amines, alkanol amines and mixed alkylalkanol amines, and at least one water-soluble compound the anion portion of which is of exo-cis configuration and conforms to the structure in which R represents an alkyl radical selected from the group consisting of primary and secondary alkyl radicals having from 1 to 8 carbon atoms.

9. The method of claim 8 in which said salt is an ammonium sulfate.

10. The method of claim 9 in which said salt is ammonium sulfate.

11. A method for regulating the growth characteristics of a plant, comprising applying to said plant a plant response composition comprising a salt of a strong mineral acid with at least one of the group consisting of ammonia, alkyl amines, alkanol amines and mixed alkylalkanol amines, and at least one compound which when in the presence of water yields anions of eXo-cis configuration and conforming to the structure in which R represents an alkyl radical selected from the group consisting of primary and secondary alkyl radicals having from 1 to 8 carbon atoms.

12. A plant response composition comprising ammonium sulfate and exo-cis sodium methyl 3,6-endoxohexahydrophthalate.

13. A plant response composition comprising ammonium sulfate and exo-cis diisopropylammonium methyl 3,6-endoxohexahydrophthalate.

NATHANIEL TISCI-ILER.

No references cited. 

1. A PLANT RESPONSE COMPOSITION COMPRISING A SALT OF A STRONG MINERAL ACID WITH AT LEAST ONE OF THE GROUP CONSISTING OF AMMONIA, ALKYL AMINES, ALKANOL AMINES, AND MIXED ALKYL-ALKANOL AMINES, AND AT LEAST ONE WATER-SOLUBLE COMPOUND THE ANION PORTION OF WHICH IS OF EXO-CIS CONFIGURATION AND CONFORMS TO THE STRUCTURE 